JPH0332919B2 - - Google Patents
Info
- Publication number
- JPH0332919B2 JPH0332919B2 JP59067166A JP6716684A JPH0332919B2 JP H0332919 B2 JPH0332919 B2 JP H0332919B2 JP 59067166 A JP59067166 A JP 59067166A JP 6716684 A JP6716684 A JP 6716684A JP H0332919 B2 JPH0332919 B2 JP H0332919B2
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- substrate
- metal foil
- polyamic acid
- flexible printed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000758 substrate Substances 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229920005575 poly(amic acid) Polymers 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000002966 varnish Substances 0.000 claims description 9
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- SFUVLEGIZGPPNN-UHFFFAOYSA-N (2-pyridin-2-ylacetyl) 2-pyridin-2-ylacetate Chemical compound C=1C=CC=NC=1CC(=O)OC(=O)CC1=CC=CC=N1 SFUVLEGIZGPPNN-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- -1 butyl lactone Chemical class 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は極めて耐熱性の優れたフレキシブル印
刷配線板用基板の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a substrate for a flexible printed wiring board that has extremely excellent heat resistance.
従来フレキシブル印刷配線板用基板は、ポリイ
ミドフイルムと金属箔とを接着剤層を介して接着
して製造されている。
Conventionally, substrates for flexible printed wiring boards have been manufactured by bonding a polyimide film and a metal foil through an adhesive layer.
この方法では接着剤の耐熱性が十分でないため
に、ポリイミドフイルムが本来備えている耐熱性
を十分に発揮することができず、フレキシブル印
刷配線用基板の半田耐熱性はせいぜい280℃程度
である。また半田耐熱性を上げるために耐熱性の
良好な接着剤を使用すると基板の可撓性が低下し
たり、カールしたりする等の欠点がある。このカ
ールを防止するために従来ゴムなどの可撓性の優
れた物質を配合している。従つて、耐熱性が十分
でないのは必然的な結果である。 In this method, the heat resistance of the adhesive is insufficient, so the inherent heat resistance of the polyimide film cannot be fully demonstrated, and the soldering heat resistance of flexible printed circuit boards is at most about 280°C. Furthermore, if an adhesive with good heat resistance is used to increase the solder heat resistance, there are drawbacks such as a decrease in the flexibility of the substrate and curling of the substrate. In order to prevent this curling, materials with excellent flexibility, such as rubber, have conventionally been added. Therefore, it is an inevitable result that the heat resistance is insufficient.
本発明は接着剤を使用しないフレキシブル印刷
配線板用基板の製造法を提供することを目的とす
るものである。
An object of the present invention is to provide a method for manufacturing a flexible printed wiring board substrate that does not use an adhesive.
すなわち本発明は4.4′−ジアミノジフエニルエ
ーテルとp−フエニレンジアミンとのモル比が
50:50〜10:90からなるジアミン成分とピロメリ
ツト酸二無水物を50モル%以上含む酸無水物成分
とを非プロトン性極性溶媒中で反応させて得たポ
リアミド酸ワニスを金属箔に直接塗布した後、溶
媒の除去及びイミド化を行うことを特徴とするフ
レキシブル印刷配線板用基板の製造法に関する。
That is, in the present invention, the molar ratio of 4.4'-diaminodiphenyl ether and p-phenylenediamine is
A polyamic acid varnish obtained by reacting a diamine component consisting of a ratio of 50:50 to 10:90 with an acid anhydride component containing 50 mol% or more of pyromellitic dianhydride in an aprotic polar solvent is applied directly to metal foil. The present invention relates to a method for manufacturing a substrate for a flexible printed wiring board, which comprises removing the solvent and imidizing the substrate.
本発明において4.4′−ジアミノジフエニルエー
テルとp−フエニレンジアミンとのモル比は50:
50〜10:90が好ましく、特に好ましくは35:65〜
15:85である。p−フエニレンジアミンのモル分
率が0.5より小さいとカールが著しく0.9より大き
いとポリイミド皮膜がもろく好ましくない。 In the present invention, the molar ratio of 4.4'-diaminodiphenyl ether and p-phenylenediamine is 50:
50-10:90 is preferred, particularly preferably 35:65-
It is 15:85. If the molar fraction of p-phenylenediamine is less than 0.5, curling will occur, and if it is more than 0.9, the polyimide film will be brittle, which is not preferred.
本発明において用いられるピロメリツト酸二無
水物以外の酸無水物成分としては3.3′−4.4′−ベ
ンゾフエノンテトラカルボン酸二無水物、3.3′,
4.4′−ビフエニルテトラカルボン酸二無水物、ナ
フタレンテトラカルボン酸二無水物、ペリレンテ
トラカルボン酸二無水物、ビス(3.4−ジカルボ
キシフエニル)エーテル二無水物等があり、ピロ
メリツト酸二無水物以外の酸無水物は50モル%以
内、特に25モル%以内使用するのが望ましい。 Acid anhydride components other than pyromellitic dianhydride used in the present invention include 3.3'-4.4'-benzophenonetetracarboxylic dianhydride, 3.3',
These include 4.4'-biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, bis(3.4-dicarboxyphenyl)ether dianhydride, and pyromellitic dianhydride. It is desirable to use acid anhydrides other than 50 mol% or less, particularly 25 mol% or less.
本発明において用いる非プロトン性極性溶媒と
してはN−メチル−2−ピロリドン、N,N−ジ
メチルアセトアミド、N,N−ジメチルホルムア
ミド、N,N−ジエチルホルムアミド、ジメチル
スルホキシド、スルホラン、メチルスルホラン、
テトラメチル尿素、ヘキサメチルホスホルアミ
ド、ブチルラクトン等が好ましく、これらの溶媒
を単独あるいは2種以上を混合して用いてもよい
しさらにこれらにキシレン、トルエン、ベンゼ
ン、フエノール、アセトン、メチルエチルケト
ン、ジアセトンアルコール、セロソルブ、メチル
イソブチルケトン、クレゾール、ジオキサン、シ
クロヘキサノン等の溶媒をポリアミド酸が析出し
ない範囲で添加して使用してもよい。 Examples of the aprotic polar solvent used in the present invention include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, dimethylsulfoxide, sulfolane, methylsulfolane,
Tetramethylurea, hexamethylphosphoramide, butyl lactone, etc. are preferred, and these solvents may be used alone or in combination, and xylene, toluene, benzene, phenol, acetone, methyl ethyl ketone, Solvents such as acetone alcohol, cellosolve, methyl isobutyl ketone, cresol, dioxane, and cyclohexanone may be added to the extent that polyamic acid does not precipitate.
ジアミン成分と酸無水物成分とのモル比はほぼ
等量で用いるのが好ましいが、いずれか一方の成
分が他の成分に対して10モル%以内好ましくは5
モル%以内であればよい。 The molar ratio of the diamine component and the acid anhydride component is preferably approximately equal, but one component is preferably within 10 mol% of the other component, preferably 5.
It may be within mol%.
ポリアミド酸溶液の樹脂分は10〜25重量%が好
ましく15〜20%が特に望ましい。 The resin content of the polyamic acid solution is preferably 10 to 25% by weight, particularly preferably 15 to 20%.
反応温度は−10℃〜100℃が好ましく、特に望
ましくは0〜50℃である。反応温度が−10℃より
低いとピロメリツト酸二無水物の溶解性が悪く、
また温度が低すぎるために反応の完結までに長時
間を要する。また100℃より高いとイミド化が進
みすぎ樹脂が析出するために好ましくない。 The reaction temperature is preferably -10°C to 100°C, particularly preferably 0 to 50°C. If the reaction temperature is lower than -10℃, the solubility of pyromellitic dianhydride is poor;
Furthermore, since the temperature is too low, it takes a long time to complete the reaction. Further, if the temperature is higher than 100°C, imidization will proceed too much and the resin will precipitate, which is not preferable.
金属箔としては銅箔、鉄箔、アルミ箔、ニツケ
ル箔等が用いられるが、銅箔が好ましく特に圧延
銅箔が望ましい。また金属箔の片面は接着力付与
の観点から粗面化されていることが望ましい。 As the metal foil, copper foil, iron foil, aluminum foil, nickel foil, etc. are used, but copper foil is preferred, and rolled copper foil is particularly desirable. Further, it is desirable that one side of the metal foil is roughened from the viewpoint of imparting adhesive strength.
上記の方法によつて得たポリアミド酸ワニスを
ダイス、コータ等の公知の塗布手段によつて金属
箔上に塗布した後、溶媒の沸点以下の温度で加熱
して大部分の溶媒を揮散させ、その後引続いて
200℃以上の温度で加熱してイミド化を行なわせ
る。イミド化を行なわせる際金属箔の酸化を防ぐ
ために窒素等の不活性気体中で加熱するのが望ま
しい。 After applying the polyamic acid varnish obtained by the above method onto a metal foil using a known application means such as a die or coater, heating at a temperature below the boiling point of the solvent to volatilize most of the solvent, then successively
Imidization is performed by heating at a temperature of 200°C or higher. When performing imidization, it is desirable to heat the metal foil in an inert gas such as nitrogen in order to prevent oxidation of the metal foil.
加熱して溶媒の除去、イミド化を行なわせる代
りに、ピリジン−無水酢酸等の脱水剤中に、ポリ
アミド酸を塗布した金属箔を浸漬して溶媒の除
去、イミド化を行つてもよい。 Instead of heating to remove the solvent and effect imidization, the metal foil coated with polyamic acid may be immersed in a dehydrating agent such as pyridine-acetic anhydride to remove the solvent and effect imidization.
以下本発明を実施例を用いてさらに詳細に説明
するが、本発明の範囲は以下の実施例に限定され
るものではない。 The present invention will be explained in more detail below using examples, but the scope of the present invention is not limited to the following examples.
実施例 1
温度計、撹拌器および塩化カルシウム管をつけ
た300ml4つ口フラスコに4.4′−ジアミノジフエ
ニルエーテル(以下DDEと略す)3.0g、p−フ
エニレンジアミン(以下PPDと略す)9.2gとN,
N−ジメチルアセトアミド(以下DMACと略す)
192.6gを入れ撹拌し、溶解する。この溶液を10
℃前後に保ちながらピロメリツト酸二無水物(以
下PMDAと略す)21.8gを徐々に添加した後3
時間撹拌して還元粘度2.46dl/g(溶媒DMAC、
濃度0.1g/dl音度25.0℃)のポリアミド酸ワニ
スを得た。このワニスを35μmの圧延銅箔上に塗
布した後、100℃30分、250℃10分、425℃10分熱
処理し塗膜厚さ50μmのフレキシブル印刷配線板
用基板を得た。この基板は熱処理後、カールがま
つたく見られなかつた。また350℃の半田に浸漬
してもふくれの発生はなかつた。耐屈折性を測定
したところ121回で銅箔が切断したが、ポリイミ
ド塗膜は異常がなかつた。Example 1 In a 300 ml four-necked flask equipped with a thermometer, stirrer, and calcium chloride tube, 3.0 g of 4,4'-diaminodiphenyl ether (hereinafter abbreviated as DDE) and 9.2 g of p-phenylenediamine (hereinafter abbreviated as PPD) were added. N,
N-dimethylacetamide (hereinafter abbreviated as DMAC)
Add 192.6g and stir to dissolve. Add this solution to 10
After gradually adding 21.8 g of pyromellitic dianhydride (hereinafter abbreviated as PMDA) while keeping the temperature around ℃,
Reduced viscosity 2.46 dl/g (solvent DMAC,
A polyamic acid varnish with a concentration of 0.1 g/dl (sound intensity 25.0°C) was obtained. This varnish was applied onto a 35 μm rolled copper foil, and then heat treated at 100° C. for 30 minutes, 250° C. for 10 minutes, and 425° C. for 10 minutes to obtain a substrate for a flexible printed wiring board with a coating thickness of 50 μm. This substrate did not show any curl after heat treatment. Furthermore, no blistering occurred even when immersed in solder at 350°C. When measuring refraction resistance, the copper foil broke after 121 cycles, but the polyimide coating showed no abnormalities.
実施例 2
DDE8.0g、PPD6.5gを220.3gのDMACに溶
解し、16.4gのPMDAと8.1gの3.3′,4.4′−ベン
ゾフエノンテトラカルボン酸二無水物の混合物を
加える以外は実施例1と同様にして還元粘度2.32
dl/gのポリアミド酸ワニスを得た。このワニス
を35μmの圧延銅箔上に塗布し、100℃30分、250
℃10分、400℃10分熱処理したところ、塗膜厚さ
50μm、曲率半径42cmのフレキシブル印刷配線板
用基板を得た。この基板を350℃の半田に浸漬し
たところふくれの発生は見られなかつた。また耐
屈折性は138回であつた。Example 2 Example except that 8.0 g of DDE and 6.5 g of PPD are dissolved in 220.3 g of DMAC and a mixture of 16.4 g of PMDA and 8.1 g of 3.3',4.4'-benzophenonetetracarboxylic dianhydride is added. Same as 1, reduced viscosity 2.32
A polyamic acid varnish of dl/g was obtained. This varnish was applied onto a 35 μm rolled copper foil, and heated at 100°C for 30 minutes at 250°C.
After heat treatment at ℃10 minutes and 400℃ for 10 minutes, the coating film thickness
A flexible printed wiring board substrate with a diameter of 50 μm and a radius of curvature of 42 cm was obtained. When this board was immersed in solder at 350°C, no blistering was observed. Moreover, the refraction resistance was 138 times.
比較例 1
35μmの圧延銅箔にエポキシ系接着剤を塗布し、
50μm厚のカプトンフイルム(デユポン社のポリ
イミドフイルム)とラミネートしフレキシブル印
刷配線板用基板を得た。この基板を300℃の半田
に浸漬したところ多数のふくれが発生した。Comparative example 1 Apply epoxy adhesive to 35μm rolled copper foil,
It was laminated with a 50 μm thick Kapton film (polyimide film manufactured by DuPont) to obtain a substrate for a flexible printed wiring board. When this board was immersed in solder at 300°C, numerous blisters occurred.
比較例 2
DDE15.0g、PPD2.7g、PMDA21.8g、
DMAC223.8gを用いる以外は実施例1と同様に
して還元粘度2.63dl/gのポリアミド酸ワニスを
得た。このワニスを35μmの圧延銅箔上に塗布し
た後、実施例2と同様に熱処理したところ、得ら
れた基板は著しくカールし、使用に耐えないもの
であつた。Comparative example 2 DDE15.0g, PPD2.7g, PMDA21.8g,
A polyamic acid varnish having a reduced viscosity of 2.63 dl/g was obtained in the same manner as in Example 1 except that 223.8 g of DMAC was used. When this varnish was applied onto a 35 μm rolled copper foil and then heat treated in the same manner as in Example 2, the resulting substrate curled significantly and was unusable.
本発明によつて得られるフレキシブル印刷配線
板用基板は、カールが小さく、可撓性があり、ま
た、耐熱性も良好である。
The flexible printed wiring board substrate obtained by the present invention has little curl, is flexible, and has good heat resistance.
Claims (1)
エニレンジアミンとのモル比が50:50〜10:90か
らなるジアミン成分とピロメリツト酸二無水物を
50モル%以上含む酸無水物成分とを非プロトン性
極性溶媒中で反応させて得たポリアミド酸ワニス
を金属箔に直接塗布した後、溶媒の除去及びイミ
ド化を行うことを特徴とするフレキシブル印刷配
線板用基板の製造法。1 A diamine component consisting of a molar ratio of 4.4'-diaminodiphenyl ether and p-phenylenediamine of 50:50 to 10:90 and pyromellitic dianhydride.
Flexible printing characterized by directly coating a metal foil with a polyamic acid varnish obtained by reacting an acid anhydride component containing 50 mol% or more in an aprotic polar solvent, followed by removal of the solvent and imidization. A method for manufacturing circuit board substrates.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6716684A JPS60210894A (en) | 1984-04-04 | 1984-04-04 | Method of producing substrate for flexible printed circuit board |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6716684A JPS60210894A (en) | 1984-04-04 | 1984-04-04 | Method of producing substrate for flexible printed circuit board |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60210894A JPS60210894A (en) | 1985-10-23 |
JPH0332919B2 true JPH0332919B2 (en) | 1991-05-15 |
Family
ID=13337036
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6716684A Granted JPS60210894A (en) | 1984-04-04 | 1984-04-04 | Method of producing substrate for flexible printed circuit board |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60210894A (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3684307D1 (en) * | 1985-10-31 | 1992-04-16 | Mitsui Toatsu Chemicals | FLEXIBLE LAMINATE FOR BOARD FOR PRINTED CIRCUITS AND METHOD FOR THE PRODUCTION THEREOF. |
JP2603927B2 (en) * | 1987-01-14 | 1997-04-23 | 鐘淵化学工業株式会社 | Manufacturing method of new polyimide resin |
JPS63175026A (en) * | 1987-01-14 | 1988-07-19 | Kanegafuchi Chem Ind Co Ltd | Novel polyamic acid copolymer |
JPS63175024A (en) * | 1987-01-14 | 1988-07-19 | Kanegafuchi Chem Ind Co Ltd | Novel polyimide copolymer and production thereof |
JP2573595B2 (en) * | 1987-03-09 | 1997-01-22 | 鐘淵化学工業株式会社 | Polyimide film |
JPS63254130A (en) * | 1987-04-10 | 1988-10-20 | Mitsubishi Electric Corp | Copolymer of aromatic polyamic acid or ester thereof |
JP2680816B2 (en) * | 1987-07-15 | 1997-11-19 | 鐘淵化学工業株式会社 | Flexible printed circuit board |
JPH0346292A (en) * | 1989-07-14 | 1991-02-27 | Kanegafuchi Chem Ind Co Ltd | Flexible printed board and manufacture thereof |
US5196500A (en) * | 1990-12-17 | 1993-03-23 | E. I. Du Pont De Nemours And Company | Tetrapolyimide film containing benzophenone tetracarboxylic dianhydride |
JPH0551453A (en) * | 1991-08-22 | 1993-03-02 | Kanegafuchi Chem Ind Co Ltd | Polyamic acid copolymer, polyimide copolymer consisting of the same copolymer and polyimide film and production thereof |
JP2831867B2 (en) * | 1991-08-28 | 1998-12-02 | 鐘淵化学工業株式会社 | Polyamic acid copolymer, polyimide copolymer comprising the same, polyimide film, and methods for producing them |
JPH06334204A (en) * | 1993-05-21 | 1994-12-02 | Ind Technol Res Inst | Preparation of flexible amorphous silicon solar cell |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS557805A (en) * | 1978-06-30 | 1980-01-21 | Ube Ind Ltd | Preparation of polyimide molded articles |
-
1984
- 1984-04-04 JP JP6716684A patent/JPS60210894A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS557805A (en) * | 1978-06-30 | 1980-01-21 | Ube Ind Ltd | Preparation of polyimide molded articles |
Also Published As
Publication number | Publication date |
---|---|
JPS60210894A (en) | 1985-10-23 |
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